J. Chem. Eng. Data
54
ative in NaCIO, systems and positive (at low concentrations) in CF,COONa systems. Probably the first observation may be related to the Na' C3H403 interaction, and the second one to the CF, CF, interaction. The value of ATlm extrapolated to m = 0 is 7.8 K mol-' kg (NaCIO, solute) and 6.0 K mol-' kg (CF,COONa solute). The second value is less reliable owing to the shape of the curve. The melting point given in this note does not agree with the value reported in the literature (76); this difference may be a consequence of different purity of the sample employed. From the values TIK = 309.4 and K, = 7.8 K mol-' kg, AH = 9.0 kJ/mol is obtained. Important supercooling phenomena were not observed: only without agitation the mixture with CF,COONa supercools as much as 10 K in the concentration range, X(CF,COONa) 0.45. Registry No. CF,COONa, 2923-18-4;NaCIO,, 7601-89-0;KCIO,,
1987, 32,54-56 Castellani, F.; Berchiesi, G.; Pucciarelli, F.; Bartocci. V. J. Chem. Eng. Data 1982, 2 7 , 65. Berchiesi, G.; Gioia Lobbia, G.; Bartoccl, V.; Vitaii, G. Thermochim. Acta 1983. 7 0 . 317. Gioia Lobbia, G:; Berchiesi, G.; Poetl, G. Thermochim , Acta 1984, 7 4 ,
- -
7778-74-7:1,3-dioxolan-2-one, 96-49-1.
247. Gioia Lobbia, G ; Berchiesi, G.: Poeti. G. Thermochim Acta 1984, 7 8 ,
297. Gioia Lobbia, G.; Berchiesi, G. Thermochim. Acta 1984, 7 2 , 391. Gioia Lobbia, G.;Berchiesi, G. Thermochim. Acta 1984, 7 4 , 251. Gioia Lobbia, G.; Amico, A. Thermochim Acta 1985, 8 7 , 257. Miyake, M.; Kaji, 0.; Nakagaura, N.; Suzuki, T. J Chem. SOC., Fara day Trans. 2 1985, 8 1 , 277. Ohtaki, H.: Fumaki, A,; Rode, B. M.; Reibuegger. G J. Bull. Chem. SOC. Jpn. 1983. 56, 2116. Berchiesi, G.;Mali, G.; Passamonti, P.:Plowiec, R. J. Chem. SOC., Faraday Trans. 2 1983, 7 9 , 1257. Plowiec, R.; Amico, A.; Berchiesi, G. J. Chem. SOC.,Faraday Trans. 2 1985, 8 1 , 217. Berchlesi, G.; Vitali, G.; Amico, A. J. Mol. Liq. 1986,3 2 , 99. Braghetti, M.; Leonesi, D.; Franzosinl, P. Ric. Sci. 1968, 3 8 , 116. Sinistri, C.; Franzosini, P. Ric. Sci. 1963, 33, 419. Weast, R . C., Ed. CRC hbndbook of Chemistry and Physics, 60th ed.; CRC Press: Boca Raton, FL, 1979;p 278.
Literature Cited (1) Castellani, F.; Berchiesi, G.; Pucciarelli, F.; Bartocci, V. J. Chem. Eng. Data 1981, 26, 150.
Received for review January 28, 1986. Revised June 4, 1986. Accepted July 10,1986.
Shear Viscosities of Binary Mixtures of Acrylonitrile -t Cyclohexane, Benzene, p -Xylene, and Mesitylene at 307.4 K R. R. Yadava" and S. S. Yadavat Chemistry Department, Gorakhpur Universiw, Gorakhpur 273 009, India
Vlscosltles of binary mixtures of acrylonitrile and nonpolar solvents (vlz., cyclohexane, benzene, p -xylene, and mesitylene) have been measured at 307.4 K. The mixture viscosltles show a marked negative deviation when the mlxture is prepared wRh cyclohexane. However, this deviation has been found to gradually reduce in the case of benzene, p-xylene, and mesitylene. The parameter d has been calculated from the vlscosity data and ha8 been found to be a minimum (mod negative value) in the case of cyclohexane. I t Increases gradually for benzene, p-xylene, and mesitylene. The values of Interchange have also been calculated and have been energy ( W,) found to show the opposite trend to that shown by the parameter d , Le., most positive with cyclohexane, less positive with benzene, and negative and more negative with p -xylene and mesitylene, respectively.
Introduction Various attempts have been made to correlate the extent of deviation of viscosity from its rectilinear dependence on the mole fractions and the values of the parameter d with the type and the degree of molecular interactions ( 7 -4). The molecular interactions between acrylonitrile and some nonpolar aromatics have been already studied in our earlier papers (5,6) by estimation of the dipole moments and it has been suggested that Present address: Chemistry Department, Garhwal University Campus, Pauri (Garhwai), India.
the complex formation is governed by dipole-induced dipole electrostatic attractions. In order to confirm the earlier conclusion and to establish the suitability of the viscosity measurements for the study of such systems, it has been felt necessary to employ viscosity measurements for the system already studied by dielectric constant measurements. Experimental Sectlon
+
The binary systems studied were acrylonitrile cyclohexane, acrylonitrile benzene, acrylonitrile p -xylene, and acryionitrile mesitylene. Acrylonitrile (B.D.H., L.R.), cyclohexane (B.D.H., L.R.), benzene (spectroscopic grade), and p-xylene and mesitylene (E. Merck) were used. All the chemicals, except that of spectroscopic grade, were purified before use and their purity was checked by density measurements. The dynamic viscosities (v), of the liquids and liquid mixtures were measured at 307.4 f 0.01 K as described elsewhere (7). The values of the viscosity were accurate within 0.01 % . The densities of the liquids and liquid mixtures were measured pycnometrically. Precautions were taken to avoid losses due to evaporation. The density values were correct to fO.OOO 1 g mL-'. Values of the parameter d for each sample of all the mixtures were calculated by eq 1, first suggested by Grunberg and
+
+
In q r 2 = x , In q r
+
-+ x p In q2 + x,x2d
(1)
Nissan ( 8 ) ,where q1,v2and xl, x 2 are the viscosities and mole fractions respectively of the components 1 and 2. vI2 is the viscosity of the liquid mixture. The parameter d is proportional
0021-9568/87/1732-0054$01.50/0 0 1987 American Chemical Society
Journal of Chemicaland Engineering Data, Vol. 32, No. 1, 1987 55
Table I. Mole Fraction of Acrylonitrile (Xz), Viscosity (q), d , and Wsiw Values at 307.4 for the Acrylonitrile-Cyclohexane System X O
0.0000 0.0861 0.2848 0.5332 0.5440 0.7114 0.8989 1.0000
n. cP
e mL-*
O.
0.7647 0.7630 0.7653 0.7672 0.7682 0.7723 0.7824 0.7871
0.760 0.660 0.530 0.419 0.396 0.359 0.318 0.309
WVieC9
d
kcal mol-'
-0.81 -0.51 -0.46 -0.65 -0.54 -0.69
1.94 1.12 0.91 1.27 0.97 1.16
1
0.2
Table 11. Mole Fraction of Acrylonitrile (Xz), Viscosity ( q ) , d , and Wdw Values at 307.4 K for the Acrylonitrile-Benzene System
x2 0.0000 0.0966 0.2512 0.4788 0.5188 0.6633 0.8844 1.0000
I
I
1
I
0.2
0.4
0.6
CP
0.530 0.494 0.448 0.395 0.386 0.357 0.320 0.309
P, g mL-'
d
kcal mol-'
0.8631 0.8585 0.8495 0.8339 0.8311 0.8197 0.8005 0.7871
-0.21 -0.17 -0.14 -0.15 -0.17 -0.27
0.51 0.41 0.32 0.33 0.35 0.54
I
1.0
MOLE FRACTION OF ACRYLONITRILE
Wvisct
7,
I
0.8
Figure 1. Variation of viscosity at 307.4 K with mole fraction of acrylonitrile in acrylonitrile-cyclohexane mixture.
c
0.6
Table 111. Mole Fraction of Acrylonitrile (Xz), Viscosity ( q ) , d , and Wd,c Values at 307.4 K for the Acrylonitrile-n -Xylene System X9
n. CP
0.0000 0.1092 0.3082 0.5430 0.6189 0.7270 0.9097 1.0000
0.539 0.510 0.469 0.414 0.394 0.368 0.329 0.309
O.
e mL-'
0.8486 0.8450 0.8389 0.8277 0.8230 0.8152 0.8020 0.7871
wvi,,
d
kcal mol-'
0.06 0.15 0.15 0.13 0.12
0.14 -0.39 -0.41 -0.35 -0.31 -0.42
0.15
Table IV. Mole Fraction of Acrylonitrile (Xz), Viscosity (q), d , and Wvi,c Values at 307.4 K for the Acrylonitrile-Mesitylene System x2
7,CP
0.0000
0.584 0.551 0.495 0.424 0.406 0.373 0.332 0.309
0.1210 0.3367 0.5736 0.6490 0.7535 0.9118 1.0000
P, g
mL-'
0.8529 0.8498 0.8409 0.8277 0.8233 0.8148 0.7997 0.7871
kcal mol-'
0.18 0.22 0.19 0.22 0.17 0.19
-0.47 -0.60 -0.56 -0.65 -0.52 -0.63
RT In (7712/TJ,)
= A W 2 [
x:!
L
I
0.2
I
I
0.4
0.6
I
0 .a
I
1.0
MOLE FRACTION OF ACRYLONITRILE
Flgure 2. Variation of viscosity at 307.4 K with mole fraction of acrylonitrile in acrylonitrile-benzene mixture. 0.8r
Wvia,,
d
to the WIRT in the two-suffix Margules equation (l), W being the interchange energy. The viscosity data were processed to obtain the value of interchange energy (W,,,,) by using the following equation Wvisc
o'21
+ A, A 2 X I ]
where the various terms carry their usual significance ( I ) . ResuHs and Dlscusslon The values of the viscosity (TJ), the parameter d , and the interchange energy ( W,,,,) as a function of composition for all the systems studied are reported in Tables I-IV. The variation of viscosities of the liquid mixtures with the mole fractions of
"'I
I
0.2
I
0.4
I
0.6
I
1
0.6
1.0
MOLE FRACTION OF ACRYLONITRILE
Figure 3. Variation of viscosity at 307.4 K with mole fraction of acrylonitrile in acrylonitrile-p-xylene mixture. acrylonitrile for all the systems studied is graphically represented in Figures 1-4. A perusal of the Figure 1 shows that there is an appreciable negative deviation from the rectilinear dependence or viscosity on mole fraction for the mixture containing cyclohexane as one of the components. The negative deviation is sufficiently reduced in the case of the acrylonitrile i-benzene system. The deviations almost vanish when p -xylene and mersitylene are
J. Chem. Eng. Data 1987,32,56-60
56 0 8-
results in a higher viscosity as compared to benzene. Apparent linear dependence of mixture viscosity on molar proportion in the case of p-xylene and mesitylene could be fortuitous. A perusal of Tables I-IV shows that the values of the pa-
02-
I
I
I
I
J
Figure 4. Variation of viscosity at 307.4 K with mole fraction of acrylonitrile in acrylonitrile-mesitylene mixture.
used as nonpolar components in the mixture. I t seems that in the case of acrylonitrile cyclohexane binary liquid mixtures, the forces between unlike molecules are far less as compared to the forces between like molecules and that is why the mixture is more fluid, Le., less viscous. This is quite likely in view of the known associating tendency of acrylonitrile. However, acrylonitrile aromatic solvent mixtures of a certain composition become less fluid, i.e., more viscous, due to enhanced intermolecular forces between unlike molecules. This enhancement coukl be due to dipole-induced dipole interaction which is proportional to the polarizability of the aromatic molecule. The values of the polarizability of p -xylene and mesitylene are higher than that for benzene; the greater interaction of acrylonitrile with the former two aromatic solvents
+
+
to dipole-induced dipole interaction. Positive d values for the mixtures with p -xylene and mesitylene seem to be due to enhanced dipole-induced dipole interaction on account of higher polarizability of the methyl-substituted benzenes. The values of W,,, have the following trend; highly positive
ports the same contention as derived from d values. Registry No. acrylonitrile, 107-13-1; cyclohexane, 110-82-7; benzene, 7 1-43-2; p -xylene, 106-42-3: mesitylene, 108-67-8.
Literature Clted (1) Grunberg, L. Trans. Faraday SOC. 1954, 5 0 , 1293. (2) Fort, R. J.; Moore, W. R. Trans. Faraday SOC. 1968, 6 2 , 112. (3) Raman, G. K.: Naidu, P. R.: Krishnan, V. R . Aust J . Chem. 1968, 2 7 , 2717. (4) Nigam, R. K.; Mahl, B. S. Indian J . Chem. 1971, 9 , 1255. Yadava, R. R.; Yadava, S. S. Indian J . Chem. 1978, M A , 826. (5) (6) Yadava, R. R.; Yadava, S. S. Indian J . Chem. 1979, 78A, 120. (7) Yadava, R. R.; Yadava, S. S. Indian J . Chem. 1981, 2 0 A , 221. (8) Grunberg, L.; Nissan, A. H. Nature 1949, 164, 799.
Received for review February 5, 1986. Accepted August 22, 1986. We are thankful to Prof. R. P. Rastogi for his interest in the work and for providing necessary facilities and to the University Grants Commission, New Delhi, for a Junior Fellowship to S.S.Y.
SolubiMy of Trialkyl Phosphate Adducts of Thorium Nitrate in Trialkyl Phosphate-Alkane Mixturest Robert J. Lemire" and Allan B. Campbell Whiteshell Nuclear Research Establishment, Atomic Energy of Canada Limited, Pina wa, Manitoba, Canada ROE 1LO
Phase diagrams have been determined at 25 O C for several systems of the type Th( NO&xTAP-TAP-alkane (where TAP E trialkyl phosphate and Th(NO,),*xTAP Is a solld adduct). The trimethyl phosphate (TMP) adduct has an extremely limited solubility in TMP solutions containing hexane. For the system Th( N03),*2.8TPP-TPP-n &decane (TPP = tri-n -propyl phosphate), a substantlal reglon of liquld-liquid immlsciblllty exlsts as well as an extenslve invarlant region. For the correspondlng trilsobutyl phosphate system, no region of iiquld-llquld ImmisciMHty was found. For t h TPP system, the dze of the reglon of ImmIsclbiHty was found to be slgnlficantly smaller when n-octane or 2,2,4-trlmethylpentane was used Instead of n-dodecane. No solld thorium nHrate adducts of triethyl phosphate or trl-n -butyl phosphate (TBP) could be prepared, but phase separation was found in systems contahing n -dodecane and anhydrous liquids with a TBPTh(NO,), ratio close to 3.0:l. +Issuedas AECL-8925.
Introduction There is a large body of data in the chemical literature concerning the extraction of actinides from aqueous solutions using trialkyl phosphates (1-3).Most of these data are from experiments in which a nitrate salt was partitioned between organic and aqueous phases-offen with a fixed composition mixture as the organic phase (e.g., 30% tri-n-butyl phosphate (TBP) in kerosene). The formation of a third liquid phase (Le., phase separation of the predominantly organic liquid) has been reported in many cases, most notably in thorium nitrate-TBPalkane diluent-water-nitric acid systems (4, 5). The third liquid phase can cause substantial difficulties in extraction procedures during the reprocessing of thorium fuel for nuclear reactors. There has been File systematic study of phase relationships in this five-component system, at least in part because no solid adducts of Th(NQ3), with TBP have been reported. However, solid anhydrous adducts of Th(N03), with other trialkyl phosphates have been synthesized (6, 7). Thus, we decided to carry out a detailed study of phase relationships in simple anhydrous subsystems each containing only Th(NO,),, a trialkyl phosphate (TAP) capable of forming a solid adduct with Th(NO,),, and an alkane diluent. The work was then extended
0021-956818711732-0056$0 1.5010 0 1987 American Chemical Society
